Thermoplastic resin composition, a solar cell sealing sheet, and a solar cell

ABSTRACT

The present invention provides a thermoplastic resin composition that gives a solar cell sealing sheet having, even without being crosslinked, good mechanical strength, solar cell sealability, transparency, and weatherability. 
     The thermoplastic resin composition of the present invention comprises 1 to 95% by weight of a propylene-based polymer (A) and 5 to 99% by weight of a copolymer (B) with at least one •-olefin having 2 to 20 carbon atoms other than propylene, wherein (A) satisfies the following (i) and (ii), and (B) has a melting point below 80° C. or does not show a melting point as measured by a differential scanning calorimeter (DSC). (i) Melting point measured by a differential scanning calorimeter (DSC) method is in the range of 80 to 135° C. (ii) Endotherm attributable to crystal melting is not observed at 140° C. or more in the endothermic curve measured by a differential scanning calorimeter (DSC) method.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application is a Divisional of U.S. patent application Ser. No.11/783,891, filed Apr. 12, 2007, which claims priority from JapanesePatent Application No. 2006-111069, filed Apr. 13, 2006. The contents ofthese applications are incorporated herein by reference in theirentirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to the sheet for sealing a solar cellbetween a front and a back material made of a sheet or a plate of aglass, a plastic and the like, particularly relates to a non-crosslinkedsolar cell sealing sheet capable of performing thermal lamination at lowtemperature.

2. Description of the Related Art

Conventionally, as a solar cell sealing sheet of this type, an organicperoxide-containing ethylene-vinyl acetate copolymer (abbreviated asEVA) has been generally used, since it has resin characteristics of goodflexibility, high transparency, and excellent long-term durability byblending with an appropriate additive such as a weathering stabilizer,an adhesion promoter and the like.

However, because EVA has such drawbacks as lower melting point andpoorer heat resistance that causes heat distortion at the temperaturewhere a solar cell module is used, the hest-resistance has been effectedby blending it with an organic peroxide in order to form a crosslinkedstructure.

A solar cell sealing sheet can be formed by a publicly-known sheetforming method capable of forming a polyolefin, but such a method asblending the organic peroxide has problems to cause deterioration ofhigh speed productivity since the sheet formation is forced to beperformed at low temperature in order to prevent decomposition of theorganic peroxide.

In the process for producing a solar cell having the structure of (asurface protection layer=glass, plastics)/(a solar cell sealingsheet)/(a power module=a solar cell element)/(a solar cell sealingsheet)/(a surface protection layer=glass, plastics), generally employedare two processes composed of a tentative adhesion process by thermallamination under vacuum and a crosslinking process in an oven at hightemperature. This crosslinking process by organic peroxide requiresseveral ten minutes, and therefore shortening of the crosslinkingprocess time or elimination itself is strongly requested.

Further, there exists the concern that the power generation efficiencymay be lowered by the adverse effect on a power module caused by adecomposition gas (acetic acid gas) from EVA or by the vinyl acetategroup of EVA itself.

In order to avoid the above-mentioned problems associated with EVA, asolar cell sealing sheet employing an ethylene-•-olefin copolymer(Japanese Patent Laid-Open Publication No. 2000-91611) was proposed. Ithas been considered that these materials may reduce the adverse effectson a power module, but the balance between heat resistance andflexibility was not sufficiently good, and in addition, good heatresistance could not be realized without crosslinking, so that it hasbeen difficult to eliminate the crosslinking process.

Inventors of the present invention have tackled the development of asolar cell sealing sheet usable even without being crosslinked, based onpolypropylene or a copolymer mainly composed of propylene havingexcellent heat resistance. As a result of investigation by the presentinventors, it has become clear that, although the solar cell sealingsheet based on such polypropylene or a copolymer mainly composed ofpropylene has good flexibility and heat resistance, there exist problemsthat the applicable temperature range for thermal lamination (process toadhere or fuse by heating a stack of a solar cell power module, a solarcell sealing sheet of the present invention, and further a glass or aback sheet) during solar cell manufacturing is very narrow.

During thermal lamination, low temperature as possible (specifically160° C. or less, or more preferably below 160° C.) is preferred forthermal lamination, since a power module constituting theabove-mentioned solar cell and a surface protection layer are damaged athigh temperature.

In Japanese Patent Laid-Open Publication No. H11-163377, thermallamination of a transparent resin between 120° C. and 160° C. is alsodescribed.

SUMMARY OF THE INVENTION

By investigation of the present inventors, it has become clear that,when a material based on polypropylene or a copolymer mainly composed ofpropylene is heated at the neighborhood temperature of the meltingpoint, cloudiness is generated, and thus transparency of a solar cellsealing sheet using this material is seriously damaged. Therefore, thepresent inventors considered that to develop a non-crosslinked solarcell sealing sheet satisfying both heat resistance and thermallamination properties at low temperature by solving these problems wasthe subject.

An object of the present invention is to provide a thermoplastic resincomposition and a solar cell sealing sheet comprised thereof havingsufficient heat resistance for practical use with a property thatcloudiness is not generated by thermal lamination at low temperature,while retaining flowability in the extent of allowing for molding.

A first thermoplastic resin composition of the present inventioncomprises 1 to 95% by weight of a propylene-based polymer (A) and 5 to99% by weight of a propylene-based copolymer (B) with at least one•-olefin having 2 to 20 carbon atoms other than propylene, wherein (A)has the following characteristics of (i) and (ii), and (B) has a meltingpoint below 80° C. or does not show a melting point as measured by adifferential scanning calorimeter (here, the sum of (A) and (B) is 100%by weight). Characteristics of a propylene-based polymer (A):

-   (i) Melting point measured by a differential scanning calorimeter    (DSC) method is in the range of 80 to 135° C.-   (ii) Endotherm attributable to crystal melting is not observed at    140° C. or more in the endothermic curve measured by a differential    scanning calorimeter (DSC) method.

In the first thermoplastic resin composition of the present invention,it is preferable for a propylene-based polymer (A) to further satisfythe following (iii).

-   (ii) Melting point (Tm) measured by a differential scanning    calorimeter (DSC) and Vicat softening temperature (Tv) measured in    accordance with ASTM D1525 satisfy Equation (I):    0.234×(Tm)^(1.277) ≦Tv≦Tm  Equation (I)

(here, Tm is in the range of 80 to 135° C.).

The first thermoplastic resin composition of the present invention maycontain 0.1 to 5 parts by weight of a coupling agent (Y) relative tototal 100 parts by weight of the propylene-based polymer (A) and thepropylene-based copolymer (B).

It is preferable that the first thermoplastic resin compositionmentioned above has 0.05 g/10 min or more of MFR at 230° C.

A thermoplastic resin composition obtained by melt-kneading a mixture,comprising 1 to 95% by weight of the propylene-based polymer (A) and 99to 5% by weight of the propylene-based copolymer (B) (the sum of (A) and(B) is 100% by weight), and 0.1 to 5 parts by weight of the couplingagent (Y) relative to 100 parts by weight of the sum of (A) and (B) inthe presence of an organic peroxide is one preferred embodiment of thepresent invention (hereinafter it may be called as “the secondthermoplastic resin composition”). It is preferable that the secondthermoplastic resin composition has 0.05 g/10 min or more of MFR at 230°C.

Both of these first and second thermoplastic resin compositions aresuitably used for solar cell sealing. A solar cell sealing sheet of thepresent invention comprises the first or the second thermoplastic resincomposition.

A solar cell of the present invention comprises using theabove-mentioned solar cell sealing sheet.

A third thermoplastic resin composition of the present inventioncomprises 1 to 95% by weight of a propylene-based polymer (AA) and 5 to99% by weight of a propylene-based copolymer (BB) with at least one•-olefin having 2 to 20 carbon atoms other than propylene, wherein (AA)satisfies the following (ia) and (iia) and (BB) has a melting pointbelow 80° C. or does not show a melting point as measured by adifferential scanning calorimeter (DSC) method.

-   (ia) A melting point measured by a differential scanning calorimeter    (DSC) method is 80° C. or more and 140° C. or less.-   (iia) Molecular weight distribution obtained by a gel permeation    chromatography (GPC) is 3 or less.

In the third thermoplastic resin composition of the present invention,the propylene-based copolymer (BB) is preferably apropylene-ethylene-•-olefin copolymer (BB-1);

A propylene-ethylene-•-olefin copolymer (BB-1) comprises 45 to 92 mol %of the constituent unit derived from propylene, 5 to 25 mol % of theconstituent unit derived from ethylene, and 3 to 30 mol % of theconstituent unit derived from an •-olefin having 4 to 20 carbon atoms,and has its melting point below 80° C. or does not show a melting pointas measured by a differential scanning calorimeter.

In the third thermoplastic resin composition of the present invention,0.1 to 5 parts by weight of a coupling agent (Y) may be blended relativeto 100 parts of the sum of the propylene-based polymer (AA) and thepropylene-based copolymer (BB).

It is preferable that the third thermoplastic resin composition of thepresent invention has 0.05 g/10 min or more of MFR at 230° C.

The third thermoplastic resin composition is suitably used for solarcell sealing.

Another solar cell sealing sheet of the present invention comprises thethird thermoplastic resin composition.

Another solar cell of the present invention comprises using theabove-mentioned solar cell sealing sheet formed from the thirdthermoplastic resin composition of the present invention.

By using the first or the second thermoplastic resin composition of thepresent invention, a solar cell sealing sheet having sufficiently goodheat resistance for practical use with a property that cloudiness is notgenerated by thermal lamination at low temperature, while retainingflowability in the extent of allowing for molding, can be provided. Byusing this solar cell sealing sheet, the applicable temperature rangefor thermal lamination during the solar cell manufacturing is widened,and specifically, damage to other members (a power module or a surfaceprotection layer) can be reduced since thermal lamination can beperformed at lower temperature. Furthermore, since the crosslinkingprocess causing deterioration of resin flowability is not necessary foreffecting the heat resistance, the time for solar cell manufacturingprocess can be shortened significantly and also the recycling of thesolar cell after use can be easier. In addition, the first thermoplasticresin composition blended with the coupling agent (Y) becomes athermoplastic resin composition having excellent adhesive propertieswith an objective material as well. The second thermoplastic resincomposition also becomes a thermoplastic resin composition havingexcellent adhesive properties with an objective material.

By using the third thermoplastic resin composition of the presentinvention, a solar cell sealing sheet having sufficiently good heatresistance for practical use with a property that cloudiness is notgenerated by thermal lamination at low temperature, while retainingflowability in the extent of allowing for molding, can be provided. Byusing this solar cell sealing sheet, the applicable temperature rangefor thermal lamination during the solar cell manufacturing is widened,and specifically, damages to other members (a power module or a surfaceprotection layer) can be reduced since thermal lamination can beperformed at lower temperature. Furthermore, since the crosslinkingprocess causing deterioration of resin flowability is not necessary foreffecting the heat resistance, the time for solar cell manufacturingprocess can be shortened significantly and also the recycling of thesolar cell after use can be easier.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the DSC curve when the temperature is raised from −150° C.to 200° C. for the propylene-based polymer (A-1) used in Example at theheating rate of 20° C./min.

FIG. 2 shows the DSC curve for the propylene-based polymer (A-2) used inExample.

FIG. 3 shows the DSC curve for the propylene-based polymer (A-3) used inExample.

FIG. 4 shows the DSC curve for the propylene-based polymer (A-4) used inExample.

FIG. 5 shows one embodiment in which the solar cell sealing sheet of thepresent invention is applied.

FIG. 6 shows the samples used for heat resistance test in Example 11 andComparative Example 11.

FIG. 7 shows the samples used for the glass-adhesion test in Example 11and Comparative Example 11.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The First and Second Thermoplastic Resin Compositions, a Solar CellSealing Sheet Using the Compositions Thereof, and a Solar Cell Using theSolar Cell Sealing Sheet Thereof

(A) A Propylene-Based Polymer

As a propylene-based polymer used in the present invention, there may bementioned a propylene homopolymer or a copolymer of propylene with atleast one •-olefin having 2 to 20 carbon atoms other than propylene.Here, examples of the •-olefin having 2 to 20 carbon atoms other thanpropylene include ethylene, 1-butene, 1-pentene, 1-hexene,4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene, 1-eicosene and the like, though a copolymerwith ethylene and/or an •-olefin having 4 to 10 carbon atoms may bepreferably used.

The constituent unit derived from •-olefins in the polypropylene may be35 mol % or less, preferably 20 mol % or less (here, the sum of theconstituent unit derived from propylene and the constituent unit derivedfrom •-olefin (other than propylene) is 100 mol %). Further two or morekinds of the constituent units derived from the •-olefins other thanpropylene may be contained.

These •-olefins may form a random or a block copolymer with propylene,though a random copolymer may be preferably used in the presentinvention.

As mentioned above, in the present invention a random copolymer ofpropylene with an •-olefin having 2 to 20 carbon atoms (other thanpropylene) is preferred, wherein the amount of the constituent unitderived from •-olefin having 2 to 20 carbon atoms is preferably 1 to 7.5mol %, more preferably 2 to 7 mol %, and further preferably 2.5 to 6.5mol %.

Further, a propylene-based polymer (A) has desirably the melt flow rate(MFR) of 0.01 to 1000 g/10 min, and preferably 0.05 to 100 g/10 min asmeasured at 230° C. under a load of 2.16 kg in accordance with ASTMD1238.

The melting point (the peak of the endothermic curve showing melting ofpropylene-based polymer crystals) of the propylene-based polymer (A) ofthe present invention as measured by a differential scanning calorimeter(DSC) is in the range of 80 to 135° C., preferably 100 to 135° C., morepreferably 110 to 130° C., and particularly preferably 115° C. to 130°C.

In the propylene-based polymer (A) of the present invention, theendotherm due to crystal melting is not observed at 140° C. or more inthe endothermic curve as measured by a differential scanning calorimeter(DSC) method. Here, the methods for measuring melting point and forconfirmation of whether or not the endotherm at 140° C. or more existsare as those described in “(1) Melting point and confirmation ofpresence or absence of the endotherm at 140° C. or more” in Examples.

Here, the phrase “the endotherm due to crystal melting is not observed”is defined as follows.

Namely, dried alumina packed in the same aluminum pan as the onedescribed in 1-1) of the above-mentioned “(1) Melting point andconfirmation of presence or absence of the endotherm at 140° C. or more”is prepared as the reference, and then the vertical axis value (heatquantity) of the endothermic curve obtained according to the conditionsof (i) to (iii) in the above-mentioned 1-1) is taken as follows.

D_(top)=the vertical axis value at the peak point of melting point(maximum melting point)

D₁₄₀° C.=the vertical axis value at 140° C.

D₁₀₅° C.=the vertical axis value at 150° C.

Further, D1 and D2 are defined as below, and when they satisfy Equation(1) or preferably Equation (1′), it means that the endotherm due tocrystal melting is not observed at 140° C. or more.D1=D _(top) −D ₁₅₀° C.D2=D ₁₄₀° C.−D ₁₅₀° C.D2/D1≦0.05  Equation (1)D2/D1≦0.03  Equation (1′)

Here, D2 may take a negative value.

Here, the DSC measurement conditions to confirm melting point and thequantity of heat of fusion are those described in Examples.

A propylene-based polymer (A) has the tensile modulus of usually 600 MPaor more, preferably 700 MPa or more, and more preferably 750 MPa or moreas measured at 23° C. by using a dumbbell in accordance with JISK7113-2, the chuck distance of 80 mm, and the tensile rate of 200mm/min, though the modulus is not particularly restricted to thesevalues.

The sample for the measurement is the press sheet obtained byhot-pressing a sample at 190° C. between the upper and the lower SUSmolds with 4-mm thickness, followed by rapid cooling with a coolingchiller of 20° C. for molding, then kept for 72 hours or longer.

The propylene-based polymers (A) of the present invention are suitablythose whose melting point (Tm) measured by a differential scanningcalorimeter (DSC) and Vicat softening temperature (Tv) measured inaccordance with ASTM D1525 satisfy the following Equation (2) orpreferably Equation (2)′.0.234×(T)^(1.277) ≦Tv≦Tm  Equation (2)0.234×(T)^(1.277) ≦Tv≦0.902×(Tm)^(1.011)  Equation (2)′:(here, Tm is between 80° C. and 135° C.).

The propylene-based polymer (A) having (i) melting point of 135° C. orless and satisfying the above-mentioned (ii) indicates that it has anarrow composition distribution, namely a narrow melting pointdistribution.

The thermoplastic resin composition of the present invention using suchpropylene-based polymer (A) can maintain good transparency because lesscloudiness takes place even though the temperature of the thermallamination is further lowered.

The propylene-based polymer (A) having (i) melting point of 135° C. orless and satisfying the (ii), and further the above-mentionedrelationships between melting point Tm and Vicat softening temperatureTv, means that it is composed of molecules having homogeneouscomposition distribution.

Generally, polypropylene has lower Vicat softening temperature (Tv) thanmelting point (Tm), and especially polypropylene with wider compositiondistribution tends to have larger difference between melting point Tmand Vicat softening temperature Tv. On the contrary, Tm and Tvsatisfying the above equations (the difference between melting point Tmand Vicat softening temperature Tv is small) means that thepropylene-based polymer (A) has a very narrow composition distribution.

The sample for the measurement of the Vicat softening point is the presssheet that is obtained by hot-pressing a sample at 190° C. between theupper and the lower SUS molds with 4-mm thickness, followed by rapidcooling with a cooling chiller of 20° C. for molding, then kept for 72hours or longer.

The thermoplastic resin composition of the present invention using suchpropylene-based polymers (A) can maintain good transparency becausecloudiness does not take place even though the thermal lamination isperformed at the neighborhood temperature of the melting point (namelyaround at 150° C.).

As a reason for this, it is speculated that such propylene-based polymer(A) does not contain a component with high-melting point (namely acomponent showing the endotherm at 135° C. or more) because of ahomogeneous composition distribution, and thus its crystalline lamellaand crystalline domain size formed by crystallization becomehomogeneous.

The propylene-based polymer (A) of the present invention may be usedeither in isotactic or syndiotactic structures. In addition, pluralpropylene-based polymers (A) may be used in combination as appropriate,and for instance, two or more kinds of components having differentmelting point, rigidity, or molecular weight may be also used.

The above-mentioned propylene-based polymer (A) is obtained bypolymerizing propylene or copolymerizing propylene with other •-olefinby using a Ziegler catalyst composed of solid catalyst componentcontaining, for example, magnesium, titanium, halogen and anelectron-donor as essential components, an organoaluminum compound, andan electron-donors, or by using a metallocene catalyst composed of ametallocene compound as one component, though the polymer obtained byusing a metallocene catalyst system composed of a metallocene compoundas one component can be preferably used as the propylene-based polymer(A) having the above-mentioned characteristics.

As the metallocene catalyst to be used, a metallocene catalyst composedof a publicly-known metallocene compound capable of polymerizing an•-olefin, an organoaluminum oxy-compound and/or a compound capable offorming an ion pair by reacting with a metallocene compound may bementioned, but a metallocene catalyst capable of performing astereoregular polymerization affordable such structures as isotactic orsyndiotactic structure and the like may be preferably mentioned. Forinstance, they can be produced by using the catalysts described in thepamphlet of International Publication WO 2001-27124 and in JapanesePatent Laid-Open Publication No. 2006-52313. Preferred specific examplesof the •-olefin used for copolymerization with propylene includeethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octeneand the like.

A commercially available polymer may be also used as (A). For example, apropylene-based polymer (A) that satisfies Equation (2), preferablyEquation (2)′, may be produced by fractionally removing a component withlow melting point from a propylene-based polymer that does not satisfyEquation (2).

(B) A Propylene-Based Copolymer

The propylene-based copolymers (B) of the present invention is acopolymer of propylene with at least one •-olefin having 2 to 20 carbonatoms other than propylene and have melting point below 80° C. or do notshow melting point as measured by a differential scanning calorimeterDSC. Here, the phrase “do not show melting point” means that the crystalmelting peak with the heat of crystal melting of 1 J/g or more is notobserved between −150 to 200° C. The measurement conditions are as thosedescribed in Examples.

It is preferred that the propylene-based copolymer (B) used in thepresent invention has melting point of 60° C. or less or does not show amelting point as measured by DSC, and more preferably does not show amelting point.

In the propylene-based copolymer (B) of the present invention, an•-olefin used as a comonomer is preferably ethylene and/or an •-olefinhaving 4 to 20 carbon atoms.

The propylene-based copolymer (B) of the present invention contains 45to 92 mol % and preferably 56 to 90 mol % of a propylene unit, and 8 to55 mol % and preferably 10 to 44 mol % of an •-olefin as a comonomer.

The propylene-based copolymer (B) of the present invention desirably hasthe melt flow rate (MFR) of 0.01 to 1000 g/10 min, and preferably 0.05to 50 g/10 min as measured at 230° C. and under a load of 2.16 kg inaccordance with ASTM D1238.

As the method for producing the propylene-based copolymer (B) of thepresent invention, there is no particular restriction, but apublicly-known catalyst capable of performing stereoregularpolymerization of olefins to afford isotactic or syndiotactic structuresmay be mentioned. For example it can be produced by copolymerizingpropylene with other •-olefins in the presence of a catalyst composed ofa solid titanium component and an organometallic compound as a maincomponent, or a metallocene catalyst composed of a metallocene compoundas one catalyst component. Preferably, as described later, it isproduced by copolymerizing propylene, ethylene, and an •-olefin having 4to 20 carbon atoms in the presence of a metallocene catalyst. Forexample, a catalyst described in International Publication WO2004-087775, for example, such a catalyst described in Examples 1e to 5ein the pamphlet of said document and the like may be used.

The propylene-based copolymer (B) of the present invention is preferredto have the following properties additionally and independently.

Triad tacticity (mm fraction) as measured by ¹³C-NMR is preferably 85%or more, more preferably 85 to 97.5%, further preferably 87 to 97%,particularly preferably 90 to 97%. When the triad tacticity (mmfraction) is within this range, the polymer has particularly excellentbalance between flexibility and mechanical strength, so that it issuitable for the present invention. The mm fraction can be measured bythe method described from the line 7 of page 21 to the line 6 of page 26in the pamphlet of International Publication WO 2004-087775.

Shore A hardness of the propylene-based copolymer (B) of the presentinvention is not particularly restricted, but usually in the range of 30to 80, preferably 35 to 75.

Further, the propylene-based copolymer (B) in the present invention hasthe stress (M100) at 100%-strain of usually 4 MPa or less, preferably 3MPa or less, and more preferably 2 MPa or less as measured at 23° C. inaccordance with JIS K6301 by using JIS3 dumbbell, the span distance of30 mm and the tensile rate of 30 mm/min. When the M100 of apropylene-based copolymer (B) is in this range, it is excellent inflexibility, transparency, and rubber elasticity.

The propylene-based copolymer (B) of the present invention hascrystallinity of usually 20% or less, and preferably 0 to 15% asmeasured by X-ray diffraction. The propylene-based copolymer (B) of thepresent invention has a single glass transition temperature, and itsglass transition temperature Tg as measured by a differential scanningcalorimeter (DSC) is usually −10° C. or less, and preferably in therange of −15° C. or less.

When the glass transition temperature Tg of the propylene-basedcopolymer (B) of the present invention is in the above-mentioned range,it is excellent in cold resistance and low-temperature properties.

The propylene-based copolymer (B) of the present invention, when thereexists melting point (Tm, ° C.) in the endothermic curve of adifferential scanning calorimeter (DSC) method, has the quantity of heatof fusion •H of usually 30 J/g or less and is also subject to thefollowing equation between C3 content (mol %) and the quantity of heatof fusion •H (J/g). •H<345 Ln(C3 content mol %)−1492,

here, when there is a melting point, 70≦C3 content (mol %)≦90 is usual.

The molecular weight distribution (Mw/Mn, relative to polystyrenestandards, Mw: weight-average molecular weight, Mn: number-averagemolecular weight) of the propylene-based copolymer (B) of the presentinvention as measured by GPC is preferably 4.0 or less, more preferably3.0 or less, and further preferably 2.5 or less.

Preferred specific examples for the propylene-based copolymers (B) ofthe present invention include the following propylene-ethylene-•-olefincopolymers (B-1). By using such propylene-ethylene-•-olefin copolymers(B-1), a solar cell sealing sheet having excellent flexibility and heatresistance, mechanical strength, solar cell sealability, andtransparency is obtained. Here, the term “solar cell sealability” meansthat the cracking rate of a solar cell element (silicon cell) duringpower module setting is lowered due to excellent flexibility.

The propylene-ethylene-•-olefin copolymer (B-1) contains the constituentunit derived from propylene of 45 to 92 mol %, preferably 56 to 90 mol%, and more preferably 61 to 86 mol %, the constituent unit derived fromethylene of 5 to 25 mol %, preferably 5 to 14 mol %, and more preferably8 to 14 mol %, and the constituent unit derived from an •-olefin having4 to 20 carbon atoms of 3 to 30 mol %, preferably 5 to 30 mol %, andmore preferably 6 to 25 mol %. As an •-olefin, 1-butene is particularlypreferred.

A propylene-ethylene-•-olefin copolymer (B-1) containing the constituentunits derived from propylene, ethylene, and •-olefins having 4 to 20carbon atoms in such amounts has good compatibility with thepropylene-based polymer (A), and thus the obtained solar cell sealingsheet exerts sufficient transparency, flexibility, heat resistance, andscratch resistance.

A Thermoplastic Resin Composition, and a Solar Cell Sealing Sheet

The first thermoplastic resin composition of the present inventioncomprises the following composition of (A) and (B) in the followingblending amount.

-   (A) A propylene-based polymer of 1 to 95 parts by weight, preferably    5 to 80 parts by weight, and more preferably 10 to 50 parts by    weight-   (B) A propylene-based copolymer of 5 to 99 parts by weight,    preferably 20 to 95 parts by weight, and more preferably 50 to 90    parts by weight    Here, the sum of (A) and (B) is 100 parts by weight.

When (A) and (B) are within the above-mentioned ranges, the sheetformability is excellent, and the obtained solar cell sealing sheet isexcellent in heat resistance, transparency, and flexibility, and thus issuitable for the present invention.

Further, the thermoplastic resin composition of the present inventioncomposed of the above-mentioned (A) and (B) is preferably blended with acoupling agent as an adhesion promoter to a glass, a plastic material,and the like, and thus can be suitably used to obtain a solar cellsealing sheet for adhesion with a glass or a plastic material.

A coupling agent (Y) used in the present invention is not particularlyrestricted so far as it can improve the adhesion of the layer containingthermoplastic resin composition of the present invention with anotherlayer containing a resin having a polar group, or with another layercontaining inorganic compounds such as a metal or a glass in an amountof 50% by weight or more, but a coupling agent of a silane-type,titanium-type, and chrome-type is preferably used, and a silane-typecoupling agent (a silane coupling agent) is particularly preferred. Apublicly-known silane coupling agent can be used without particularrestriction, and specific examples include vinyl triethoxysilane, vinyltrimethoxysilane, vinyl tris(•-methoxyethoxysilane), •-glycidoxypropyltrimethoxysilane, •-aminopropyl triethoxysilane and the like. Theblending amount of a silane coupling agent is 0.1 to 5 parts by weightor preferably 0.1 to 3 parts by weight relative to 100 parts by weightof the sum of the above-mentioned (A) propylene-based polymer and (B)propylene-based copolymer.

The coupling agent (Y) may be present in the state of being grafted withat least one of (A) and (B) that constitute the thermoplastic resincomposition by using an organic peroxide. In this case, the amount ofthe coupling agent to be used is preferably about 0.1 to 5 parts byweight relative to 100 parts of the sum of the above-mentioned (A)propylene-based polymer and (B) propylene-based copolymer. The use ofthe silane-grafted thermoplastic resin composition also affords adhesionproperties to a glass or a plastic material equal to or greater thanthose of a blend containing a silane coupling agent.

When an organic peroxide is used, its amount is, for example, 0.001 to 5parts by weight, and preferably 0.01 to 3 parts by weight relative tototal 100 parts by weight of the above-mentioned (A) and (B).

A publicly-known organic peroxides can be used with no particularrestriction, and specific examples include dilauroylperoxide,1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, dibenzoylperoxide,t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate,t-butylperoxyisobutyrate, t-butylperoxymaleic acid,1,1-di(t-amylperoxy)-3,3,5-trimethylcyclohexane,1,1-di(t-amylperoxy)cyclohexane, t-amylperoxyisononanoate,t-amylperoxy-n-octoate,1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane,1,1-di(t-butylperoxy)cyclohexane, t-butylperoxyisopropylcarbonate,t-butylperoxy-2-ethylhexylcarbonate,2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-amyl-peroxybenzoate,t-butylperoxyacetate, t-butylperoxyisononanoate, t-butylperoxybenzoate,2,2-di(butylperoxy)butane, n-butyl-4,4-di(t-butylperoxy)butyrate,methylethylketone peroxide, ethyl-3,3-di(t-butylperoxy)butyrate,dicumylperoxide, t-butylcumylperoxide, di-t-butylperoxide,1,1,3,3-tetramethylbutylhydroperoxide, acetylacetoneperoxide, and thelike.

Further, in the present invention, the following auxiliary agents can beused as necessary. Specific examples of auxiliary agents include peroxyauxiliary agents such as sulfur, p-quinonedioxime,p,p′-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline,nitrosobenzene, diphenylguanizinetrimethylolpropane-N,N′-m-phenylenedimaleimide and the like; ordivinylbenzene, triallyl cyanurate (TAC), and triallyl isocyanurate(TAIC). In addition, the examples include polyfunctional methacrylatemonomers such as ethyleneglycol dimethacrylate, diethyleneglycoldimethacrylate, polyethyleneglycol dimethacrylate, trimethylolpropanetrimethacrylate, allyl methacryate and the like, and polyfunctionalvinyl monomers such as vinyl butyrate and vinyl stearate, and theothers. Among them, triallyl cyanurate (TAC) and triallyl isocyanurate(TAIC) are preferred.

In the present invention, the above-mentioned auxiliary agent is usedwith an organic peroxide in the weight ratio (auxiliary agent/organicperoxide) of 1/30 to 20/1, and preferably 1/20 to 10/1.

The first thermoplastic resin composition of the present invention maybe crosslinked but preferably non-crosslinked. Here, the term“crosslinked” means that MFR of the thermoplastic resin composition at230° C. is 0.04 g/10 min or less.

It is preferred that the first thermoplastic resin composition of thepresent invention has MFR of 0.05 g/10 min or more at 230° C.

The Second Thermoplastic Resin Composition

The second thermoplastic resin composition of the present invention isprepared by melt kneading, in the presence of the above-mentionedorganic peroxide, a mixture comprising 1 to 95% by weight of thepropylene-based polymer (A) and 5 to 99% by weight of thepropylene-based copolymer (B) (the sum of (A) and (B) is 100% by weight)with the coupling agent (Y), wherein the amount of Y is 0.1 to 5 partsby weight relative to total 100 parts by weight of (A) and (B). Forexample, two or more kinds selected from (A), (B), and (Y) arepre-blended to obtain a composition, which then may be used for meltkneading with the organic peroxide. The temperature of melt kneadingwith the organic peroxide is not particularly restricted, but it shouldbe above the temperature to initiate decomposition of the organicperoxide, and should be in such level as not to cause significantthermal deterioration of the thermoplastic resin composition, forexample, 140° C. to 300° C.

In addition, a component other than the above-mentioned (A), (B), and(Y) may be further contained in a range of amount that does not impairthe objects of the present invention. For instance, additives to bedescribed later may be included.

The second thermoplastic resin composition of the present invention maybe crosslinked, but preferably non-crosslinked. Here, the term“crosslinked” means that MFR of a thermoplastic resin composition at230° C. is 0.04 g/10 min or less.

It is preferred that the second thermoplastic resin composition of thepresent invention has MFR of 0.05 g/10 min or more at 230° C.

Various Additives

The first or the second thermoplastic resin composition of the presentinvention may be blended with various kinds of other additives. Examplesfor such additives include an UV absorber that can prevent thedeterioration due to UV rays in the sun light, a light stabilizer, anantioxidant and the like.

Specific examples of the UV absorbers include a benzophenone-type suchas 2-hydroxy-4-methoxybenzophenone, 2-2-dihydroxy-4-methoxybenzophenone,2-hydroxy-4-methoxy-4-carboxybenzophenone,2-hydroxy-4-N-octoxybenzophenone and the like, a benzotriazole-type suchas 2-(2-hydroxy-3,5-di-t-butylphenyl)benzotriazole,2-(2-hydroxy-5-methylphenyl)benzotriazole and the like, and asalicylate-type such as phenyl salicylate, p-octylphenyl salicylate, andthe like.

As the light stabilizer, a hindered amine-type is used. As theantioxidant, a hindered phenol-type and a phosphite-type are used.

As the first or second thermoplastic resin composition, the compositionhaving light transmittance (trans) of 86% or more, and preferably of 88%or more are preferably used, wherein the light transmittance is measuredby using a press sheet with 0.5-mm thickness (the both surfaces of whichare smooth by using a PET film for example (trade name “Lumiror”,manufactured by Toray Industries, Inc.) and the like as a mold releasingfilm).

The first or the second thermoplastic resin composition of the presentinvention has the melt flow rate (ASTM D1238, 230° C., 2.16 kg load) ofusually 0.05 to 1000 g/10 min, preferably 0.1 to 900 g/10 min, and morepreferably 0.5 to 800 g/10 min.

Further, in the first or the second thermoplastic resin composition ofthe present invention, the melt tension (MT) is usually 0.5 to 10 g, andpreferably 1 to 10 g. Within these ranges, moldability to form the solarcell sealing sheet of the present invention is excellent. Here, the melttension (MT) is measured at 200° C. as a tensile force applied to afilament when a strand is pulled at a constant speed (10 m/min) by usinga melt tension tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.),wherein the strand is extruded at the extrusion speed of 15 mm/min.

Into the first or second thermoplastic resin composition of the presentinvention, other additives can be added within the range that does notimpair the objects of the present invention. Examples of such additivesinclude an UV absorber for preventing deterioration due to UV rays inthe sun light, a light stabilizer, an antioxidant, a heat stabilizer, anantistatic agent, an anti-slipping agent, an anti-blocking agent, ananti-clouding agent, a transparent nucleating agent, a lubricant(silicon oil and the like), pigments, a dye, a plasticizer, an antiagingagent, a hydrochloric acid absorber, and the like.

A Solar Cell Sealing Sheet, and a Solar Cell

The solar cell sealing sheet of the present invention is, for example,the one that is comprised of the above-mentioned first or secondthermoplastic resin composition, and its thickness is, for example,preferably 0.1 mm to 3 mm, though not particularly restricted. Thisrange is preferred because a damage to a glass or a solar cell moduleduring lamination process can be reduced, and is also preferred from theviewpoint of the light transmittance and photovoltaic power generation.

A molding method to produce the solar cell sealing sheet of the presentinvention is not particularly restricted, and it can be molded by apublicly-known extrusion molding (such as cast molding, extrusion sheetmolding, inflation molding and injection molding), a press molding, acalendar molding, and the like. Further, the sheet can be embossed, bywhich its surface is decorated so that blocking of the sheets with eachother may be prevented. In addition, a damage to a glass or a solar cellmodule during lamination can be prevented, since the embossing can workas a cushion to these materials.

A power module laminated with the solar cell sealing sheet of thepresent invention on one and/or both side(s), in which a surfaceprotection layer is laminated on the outer surface of the solar cellsealing sheet as necessary, can be used as a solar cell. One exemplaryembodiment for the application of the solar cell sealing sheet is shownin FIG. 5.

The forming methods for a solar cell are not particularly restricted,and for example, it can be obtained by laminating a surface protectionlayer, a solar cell element, and a solar cell sealing sheet of thepresent invention in turn, and then hot-pressing them, for example, byaspiration under vacuum and the like.

The surface protection layer used for the front and back surfaces of thesolar cell sealing sheet of the present invention is not particularlyrestricted, and a publicly-known material can be used so long as it canprotect the layer composed of a solar cell and a solar cell sealingsheet, and does not impair the objects as a solar cell. Specificexamples of materials for the surface protection layer include not onlya glass but also such materials as a polyethylene resin, a polypropyleneresin, a cyclic polyolefin resin, an AS (acrylonitrile-styrene) resin,an ABS (acrylonitrile-butadiene-styrene) resin, an polyvinyl chlorideresin, a fluorinated resin, polyester resins such as polyethyleneterephthalate, polyethylene naphthalate, and the like, a phenolic resin,a polyacryl-type resin, polyamide resins such as various kinds ofnylons, a polyimide resin, a polyamide-imide resin, a polyurethaneresin, a cellulosic resin, a silicone-type resin, a polycarbonate resinand the like. They can be also used in a combination of plural kinds. Inaddition, with the aim to improve permeation barrier of gases and water,an inorganic/organic composite film that is vapor-deposited with aninorganic oxide etc. can be also preferably used.

In order to improve the adhesion strength between a surface protectionlayer and a solar cell sealing sheet of the present invention, andbetween plural surface protection layers themselves, a publicly-knownadhesive and an adhesive resin layers can be provided. In addition,depending on the embodiment of the solar cell of the present invention,one side of the surface protection layer may have light shielding/lightreflecting properties.

The Third Thermoplastic Resin Composition

(AA) A Propylene-Based Polymer

Examples of the propylene-based polymers (AA) used in the presentinvention include a propylene homopolymer or a copolymer of propylenewith at least one •-olefin having 2 to 20 carbon atoms other thanpropylene. Here, examples of the •-olefins having 2 to 20 carbon atomsother than propylene include ethylene, 1-butene, 1-pentene, 1-hexene,4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene, 1-eicosene and the like, though a copolymerwith ethylene and/or an •-olefin having 4 to 10 carbon atoms may bepreferably used in the present invention.

The constituent units derived from these •-olefins in the polypropylenemay be contained in the amount of 35 mol % or less, and preferably 20mol % or less. Further, the constituent unit derived from an •-olefinother than propylene may contain two or more kinds.

These •-olefins may form a random or a block copolymer with propylene,though a random copolymer may be preferably used in the presentinvention.

As mentioned above, in the present invention a random copolymer ofpropylene with an •-olefin having 2 to 20 carbon atoms (other thanpropylene) is preferred, wherein the content of the constituent unitderived from an •-olefin is preferably 1 to 7.5 mol %, more preferably 2to 7 mol %, and further preferably 2.5 to 6.5 mol %.

Further, the melt flow rate (MFR) of the propylene-based polymer (AA) asmeasured at 230° C. under a load of 2.16 kg in accordance with ASTMD1238 is desirably in the range of 0.01 to 1000 g/10 min, and morepreferably 0.05 to 100 g/10 min.

The melting point (the peak of endothermic curve that shows melting ofcrystals of a propylene-based polymer) of the propylene-based polymer(AA) of the present invention as measured by a differential scanningcalorimeter (DSC) method is 80° C. or more to 140° C. or less, morepreferably 110 to 140° C., and further preferably 110 to 135° C. DSCmeasurement conditions for confirming melting point and the quantity ofheat of fusion are those described in Examples.

Further, the propylene-based polymer (AA) of the present invention hasthe molecular weight distribution, as measured by a gel permeationchromatography (GPC), of 3 or less, preferably 1 to 2.7, and morepreferably 1.8 to 2.5.

By using the propylene-based polymer (AA) of the present inventionhaving melting point and molecular weight distribution in the aboverange, a thermoplastic resin composition that is not cloudy even whenheated at the neighborhood temperature of the melting point of (AA)(namely around 150° C.) can be obtained. Although the reasons for thisare unclear, as one of the reasons, it is inferred that thepropylene-based polymer (AA) is comprised of molecules having ahomogeneous composition distribution and the like so thatcrystallization speeds of the molecules are homogeneous, and thus it isexpected to give homogeneous crystalline lamella and crystalline domainsize when the molecules in the molten state at the neighborhoodtemperature of the melting points (namely around 150° C.) arecrystallized.

The propylene-based polymer (AA) of the present invention may be usedboth in isotactic and syndiotactic structures so long as they are wellcompatible with the propylene-based copolymer (BB) described below. Inaddition, plural propylene-based polymers (AA) can be usedsimultaneously as necessary. For example, two or more kinds ofcomponents having different melting points or rigidities may be alsoused.

These propylene-based polymers (AA) are obtained by polymerizingpropylene or copolymerizing propylene with other •-olefins in thepresence of a metallocene catalyst containing a metallocene compound asone catalyst component.

As the metallocene catalyst to be used, a metallocene catalystcomprising a publicly-known metallocene compound capable of polymerizing•-olefins and an organoaluminum oxy-compound and/or a compound capableof forming an ion pair by reacting with a metallocene compound,preferably a metallocene catalyst capable of performing a stereoregularpolymerization that can afford such structures as isotactic orsyndiotactic may be mentioned. For instance, they can be produced byusing the catalysts described in the pamphlet of InternationalPublication WO 2001-27124 and Japanese Patent Laid-Open Publication No.2006-52313. Preferred specific examples of •-olefins used for thecopolymerization with propylene include ethylene, 1-butene, 1-pentene,1-hexene, 4-methyl-1-pentene, 1-octene and the like.

(BB) A Propylene-Based Copolymer

The propylene-based copolymer (BB) of the present invention is acopolymer of propylene with at least one •-olefin having 2 to 20 carbonatoms other than propylene, having Shore A harness of 30 to 80,preferably 35 to 70, and having the melting point below 80° C. orshowing no melting point as measured by a differential scanningcalorimeter DSC. Here, the term “no melting point” means that thecrystal melting peak with the heat of crystal melting of 1 J/g or moreis not observed in the temperature range of −150 to 200° C. Themeasurement conditions are as those described in Examples.

In the propylene-based copolymer (BB) of the present invention, an•-olefin used as a comonomer is preferably ethylene and/or an •-olefinhaving 4 to 20 carbon atoms.

The propylene-based copolymer (BB) of the present invention contains 45to 92 mol %, preferably 56 to 90 mol % of a propylene unit, and 8 to 55mol %, preferably 10 to 44 mol % of an •-olefin as a comonomer to beused.

Melt flow rate (MFR) of the propylene-based copolymer (BB) of thepresent invention as measured at 230° C. under a load of 2.16 kg inaccordance with ASTM D1238 is desirably in the range of 0.01 to 1000g/10 min, preferably 0.05 to 50 g/10 min.

As the method for producing the propylene-based copolymer (BB) of thepresent invention, there is no particular restriction, but it can beproduced by copolymerizing propylene with other •-olefins in thepresence of a publicly-known catalyst capable of performingstereoregular polymerization of olefins to afford isotactic orsyndiotactic structures, for example a catalyst containing a solidtitanium component and an organometallic compound as main components, ora metallocene catalyst containing a metallocene compound as one catalystcomponent. Preferably, as described below, it is obtained bycopolymerization of propylene, ethylene, and an •-olefin having 4 to 20carbon atoms in the presence of a metallocene catalyst, and for example,a catalyst described in International Publication WO 2004-087775, forexample, a catalyst described in Examples 1e to 5e in the pamphlet ofthe said document may be used.

The propylene-based copolymer (BB) of the present invention is preferredto have the following properties additionally and independently.

Triad tacticity (mm fraction) as measured by ¹³C-NMR is preferably 85%or more, more preferably 85 to 97.5%, further preferably 87 to 97%, andparticularly preferably 90 to 97%. When the triad tacticity (mmfraction) is in this range, the balance between flexibility andmechanical strength is excellent in particular, so that it is suitablefor the present invention. The mm fraction can be measured by the methoddescribed from the line 7 of page 21 to the line 6 of page 26 in thepamphlet of International Publication WO 2004-087775.

Shore A hardness of the propylene-based copolymer (BB) of the presentinvention is not particularly restricted, but is usually in the range of30 to 80, and preferably of 35 to 75.

Further, the propylene-based copolymer (BB) of the present invention hasthe stress (M100) at 100%-strain of usually 4 MPa or less, preferably 3MPa or less, and more preferably 2 MPa or less as measured at 23° C. inaccordance with JIS K6301 by using the JIS3 dumbbell, wherein the spandistance of 30 mm and the tensile rate of 30 mm/min are employed. WhenM100 of the propylene-based copolymer (BB) is in this range, it isexcellent in flexibility, transparency and rubber elasticity.

The propylene-based copolymer (BB) of the present invention hascrystallinity of usually 20% or less, and preferably 0 to 15% asmeasured by X-ray diffraction. The propylene-based copolymer (BB) of thepresent invention has a single glass transition temperature, and itsglass transition temperature Tg as measured by a differential scanningcalorimeter (DSC) is usually −10° C. or less, and preferably in therange of −15° C. or less.

When the glass transition temperature Tg of the propylene-basedcopolymer (BB) of the present invention is in the above-mentioned range,it is excellent in cold resistance and low temperature properties.

If the propylene-based copolymer (BB) of the present invention has amelting point (Tm, ° C.) in the endothermic curve of a differentialscanning calorimeter (DSC), it usually has the quantity of heat offusion •H of 30 J/g or less and the following equation can be applied tothe relation between C3 content (mol %) and the quantity of heat offusion •H (J/g). •H<345 Ln(C3 content, mol %)−1492,

here, it is usually 76≦C3 content (mol %)≦90.

The molecular weight distribution (Mw/Mn, in terms of polystyrene, Mw:the weight-average molecular weight, Mn: the number-average molecularweight) of the propylene-based copolymer (BB) of the present inventionas measured by GPC is preferably 4.0 or less, more preferably 3.0 orless, and further preferably 2.5 or less.

Preferred specific examples of the propylene-based copolymers (BB) ofthe present invention include the following propylene-ethylene-•-olefincopolymers (BB-1). By using such a propylene-ethylene-•-olefin copolymer(BB-1), a solar cell sealing sheet having excellent flexibility and heatresistance, mechanical strength, solar cell sealability, andtransparency is obtained. Here, the term “solar cell sealability” meansthat cracking rate of a solar cell element (silicon cell) during powermodule setting is lowered due to excellent flexibility.

The propylene-ethylene-•-olefin copolymer (BB-1) contains theconstituent unit derived from propylene of 45 to 92 mol %, preferably 56to 90 mol %, and more preferably 61 to 86 mol %, the constituent unitderived from ethylene of 5 to 25 mol %, preferably 5 to 14 mol %, andmore preferably 8 to 14 mol %, and the constituent unit derived from an•-olefin having 4 to 20 carbon atoms of 3 to 30 mol %, preferably 5 to30 mol %, and more preferably 6 to 25 mol %. As to an •-olefin, 1-buteneis particularly preferred.

A propylene-ethylene-•-olefin copolymer (BB-1), comprising theconstituent units derived from propylene, ethylene, and an •-olefinhaving 4 to 20 carbon atoms in the above-mentioned amounts, has goodcompatibility with a propylene-based copolymer (AA), and thus the solarcell sealing sheet obtained exerts sufficient transparency, flexibility,heat resistance, and scratch resistance.

The Third Thermoplastic Resin Composition and a Solar Cell Sealing Sheet

The third thermoplastic resin composition of the present inventioncomprises (AA) and (BB) in the following blending amount:

-   (AA) A propylene-based polymer of 1 to 95 parts by weight,    preferably 5 to 80 parts by weight, and more preferably 10 to 50    parts by weight-   (BB) A propylene-based copolymer of 5 to 99 parts by weight,    preferably 20 to 95 parts by weight, and more preferably 50 to 90    parts by weight.    Here, the total of (AA) and (BB) is 100 parts by weight.

When the above-mentioned (AA) and (BB) are contained in the preferredrange, the sheet formability is excellent and the solar cell sealingsheet obtained is improved in heat resistance, transparency, andflexibility, and thus it is suitable for the present invention.

In addition, the thermoplastic resin composition of the presentinvention composed of the above (AA) and (BB) is blended with a couplingagent as an adhesion promoter to a glass, a plastic material and thelike, and it can be suitably used to obtain a solar cell sealing sheetfor adhesion with a glass or a plastic material.

A coupling agent (Y) used in the present invention is not particularlyrestricted so far as it can improve adhesion of the layer comprisingthermoplastic resin composition of the present invention with anotherlayer containing a resin having a polar group, or with another layercontaining such inorganic compounds as a metal or a glass in an amountof 50% by weight or more, but a coupling agent of a silane-type,titanium-type, and chrome-type is preferably used, though a silane-typecoupling agent (silane coupling agent) is suitably used. Specificexamples of the silane coupling agent, though there is no particularrestrictions, include publicly-known silane coupling agent such as vinyltriethoxysilane, vinyl trimethoxysilane, vinyltris(•-methoxyethoxysilane), •-glycidoxypropyl trimethoxysilane,•-aminopropyl triethoxysilane and the like. The amount of silanecoupling agent is 0.1 to 5 parts by weight or preferably 0.1 to 3 partsby weight relative to total 100 parts by weight of the above (AA)propylene-based polymer and (BB) propylene-based copolymer.

The coupling agent may be grafted, by using an organic peroxide, with atleast either one of (AA) or (BB) that constitutes the thermoplasticresin composition.

In this case, the amount of the coupling agent is preferably 0.1 to 5parts by weight relative to total 100 parts by weight of the above (AA)propylene-based polymer and (BB) propylene-based copolymer. The use ofthe silane-grafted thermoplastic resin composition also affords adhesionproperties to a glass or a plastic material equal to or greater thanthose obtained by the blend with a silane coupling agent.

Further, in the present invention, the following auxiliary agents can bealso used as necessary. Specific examples of auxiliary agents includeperoxy auxiliary agents such as sulfur, p-quinonedioxime,p,p′-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline,nitrosobenzene, diphenylguanizine,trimethylolpropane-N,N′-m-phenylenedimaleimide and the like, ordivinylbenzene, triallyl cyanurate (TAC), and triallyl isocyanurate(TAIC). Further, the examples include polyfunctional methacrylatemonomers such as ethyleneglycol dimethacrylate, diethyleneglycoldimethacrylate, polyethyleneglycol dimethcrylate, trimethylolpropanetrimethacrylate, allyl methacryate and the like, and polyfunctionalvinyl monomers such as vinyl butyrate and vinyl stearate, and theothers. Among them, triallyl cyanurate (TAC) and triallyl isocyanurate(TAIC) are preferred.

In the present invention, it is preferred that the above-mentionedauxiliary agent is used with the organic peroxide in the weight ratio(auxiliary agent/organic peroxide) of 1/30 to 20/1, and preferably 1/20to 10/1.

The thermoplastic resin composition of the present invention may becrosslinked but preferably non-crosslinked. Here, the term “crosslinked”means that the MFR of the thermoplastic resin composition at 230° C. is0.04 g/10 min or less.

Specific examples of the organic peroxides include, though there is noparticular restriction, publicly-known compounds such asdilauroylperoxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate,dibenzoylperoxide, t-amylperoxy-2-ethylhexanoate,t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate,t-butylperoxymaleic acid,1,1-di(t-amylperoxy)-3,3,5-trimethylcyclohexane,1,1-di(t-amylperoxy)cyclohexane, t-amylperoxyisononanoate,t-amylperoxy-n-octoate,1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane,1,1-di(t-butylperoxy)cyclohexane, t-butylperoxyisopropylcarbonate,t-butylperoxy-2-ethylhexylcarbonate,2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-amy-peroxybenzoate,t-butylperoxyacetate, t-butylperoxyisononanoate, t-butylperoxybenzoate,2,2-di(butylperoxy)butane, n-butyl-4,4-di(t-butylperoxy)butyrate,methylethylketone peroxide, ethyl-3,3-di(t-butylperoxy)butyrate,dicumylperoxide, t-butylcumylperoxide, di-t-butylperoxide,1,1,3,3-tetramethylbutylhydroperoxide, acetylacetoneperoxide and thelike.

The thermoplastic resin composition of the present invention may beblended with various kinds of other additives. Examples of suchadditives include an UV absorber that can prevent deterioration due toUV rays in the sun light, a light stabilizer, an antioxidants and thelike.

Specific examples of the UV absorbers include a benzophenone-type suchas 2-hydroxy-4-methoxybenzophenone, 2-2-dihydroxy-4-methoxybenzophenone,2-hydroxy-4-methoxy-4-carboxybenzophenone,2-hydroxy-4-N-octoxybenzophenone and the like, a benzotriazole-type suchas 2-(2-hydroxy-3,5-di-t-butylphenyl)benzotriazole,2-(2-hydroxy-5-methylphenyl)benzotriazole and the like, and asalicylate-type such as phenyl salicylate, p-octylphenyl salicylate andthe like.

As the light stabilizers, a hindered amine-type is used. And as theantioxidants, a hindered phenol-type and a phosphite-type are used.

As the third thermoplastic resin composition of the present invention,the composition having the light transmittance (trans) of 86% or more,preferably 88% or more is preferably used, wherein the lighttransmittance is measured by using a press sheet with 0.5-mm thickness(the both surfaces of which are smooth by using, for example, a PET film(trade name “Lumiror”, manufactured by Toray Industries, Inc.) and thelike as a mold releasing film).

The third thermoplastic resin composition of the present invention hasthe melt flow rate (ASTM D1238, 230° C., load 2.16 kg) of usually 0.05to 1000 g/10 min, preferably 0.1 to 900 g/10 min, and more preferably0.5 to 800 g/10 min.

Further, in the third thermoplastic resin composition of the presentinvention, the melt tension (MT) is usually 0.5 to 10 g and preferably 1to 10 g. Within these ranges, the moldability to form the solar cellsealing sheet of the present invention is excellent. Here, the melttension (MT) is measured at 200° C. as the tensile force applied to afilament when a strand is pulled at a constant speed (10 m/min) by usinga melt tension tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.,wherein the strand is extruded at the extrusion speed of 15 mm/min.

Into the third thermoplastic resin composition of the present invention,various kinds of other additives can be added within the range that doesnot impair the objects of the present invention. Examples for suchadditives include an UV absorber for preventing deterioration due to UVrays in the sun light, a light stabilizer, an antioxidant, a heatstabilizer, an antistatic agent, an anti-slipping agent, ananti-blocking agent, an anti-clouding agent, a transparent nucleatingagent, a lubricant (silicon oil and the like), pigments, a dye, aplasticizer, an antiaging agent, a hydrochloric acid absorber and thelike.

A Solar Cell Sealing Sheet and a Solar Cell

The solar cell sealing sheet of the present invention is the one havingthe thickness of, for example, 0.1 mm to 3 mm and comprised of the thirdthermoplastic resin composition. When the thickness is below this range,damage to a glass or a solar cell module tends to take place duringlamination process, and thus it is undesirable. When the thickness isabove this range, the light transmittance and the photovoltaic powergeneration become poor, and thus it is undesirable.

The forming method to produce the solar cell sealing sheet of thepresent invention is not particularly restricted, and a publicly-knownextrusion molding (such as a cast molding, extrusion sheet molding,inflation molding and injection molding), a press molding, a calendarmolding and the like can be used. Further, the sheet can be embossed, bywhich its surface is decorated so that blocking of sheets with eachother is prevented. In addition, a damage to a glass or a solar cellmodule can be prevented during lamination since the embossing can workas a cushion to these materials.

A power module laminated with the solar cell sealing sheet of thepresent invention on one and/or both side(s), in which a surfaceprotection layer is laminated on the outer surface of the solar cellsealing sheet as necessary, can be used as a solar cell. One exemplaryembodiment for the application of the solar cell sealing sheet is shownin FIG. 5.

The forming method for a solar cell is not particularly restricted, andfor example, it can be obtained by laminating a surface protectionlayer, a solar cell element, and a solar cell sealing sheet of thepresent invention in turn, and then hot-pressing them, for example, byaspiration under vacuum and the like.

A surface protection layer used for the front and back surfaces of thesolar cell sealing sheet of the present invention is not particularlyrestricted, and a publicly-known material can be used so long as it canprotect the layer composed of a solar cell and a solar cell sealingsheet, and does not impair the objects as the solar cell. Specificexamples of materials for surface protection layer include not only aglass but also such materials as a polyethylene resin, a polypropyleneresin, a cyclic polyolefin resin, an AS (acrylonitrile-styrene) resin,an ABS (acrylonitrile-butadiene-styrene) resin, a polyvinyl chlorideresin, a fluorinated resin, polyester resins such as polyethyleneterephthalate, polyethylene naphthalate and the like, a phenolic resin,a polyacryl-type resin, polyamide resins such as various kinds ofnylons, a polyimide resin, a polyamide-imide resin, a polyurethaneresin, a cellulosic resin, a silicone-type resin, a polycarbonate resinand the like. They can be used in a combination of plural kinds. Inaddition, with the aim to improve permeation barrier to gases and water,an inorganic/organic composite film that is vapor-deposited with aninorganic oxide etc. can be also preferably used.

In order to improve the adhesion strength between a surface protectionlayer and a solar cell sealing sheet of the present invention, andbetween plural surface protection layers themselves, a publicly-knownadhesive and an adhesive resin layers can be provided. In addition,depending on the embodiment of the solar cell of the present invention,one side of the surface protection layer may have light shielding/lightreflecting properties.

EXAMPLES

The present invention is explained in more detail by the followingExamples.

Evaluation Items

1. MFR

MFR was measured at 190° C. or 230° C. under a load of 2.16 kg inaccordance with ASTM D1238.

2. Transparency (Trans)

The measurement was performed in cyclohexanol by using C light source ofa digital haze meter (NDH-2000, manufactured by Nippon DenshokuIndustries Co., Ltd.) for a press sheet (reference) and a sample presssheet (reheated) prepared in the method described in Examples. The transvalue was calculated by the following equation.Trans(%)=100×(amount of total transmitted light)/(amount of incidentlight)3. Appearance (Presence or Absence of Cloudiness)

Presence or absence of cloudiness was confirmed by using the press sheet(reference) and the sample press sheet (reheated) prepared by the methoddescribed in Examples.

•: absence of cloudiness, •:slight presence of cloudiness, x: presenceof cloudiness

4. Heat Resistance (Confirmation of Fluidity of Quasi Module)

A test sample for heat resistance prepared by the method described inExample was kept in an oven at 90° C. in the state of tilting at 60°against the horizontal plane for 1000 hours to evaluate the fluidity ofa quasi module in the test sample for heat resistance.

5. Adhesiveness with a Glass (Adhesion Strength)

By using a sample for the glass adhesion test prepared by the methoddescribed in Examples, the adhesion strength with a glass was evaluated.

Raw Materials Used for the Present Invention:

Propylene-Based Polymers (A):

(A-1) A Metallocene Isotactic Propylene-Based Polymer (mPP)

A propylene-based polymer (registered trademark; WINTEC, brand name;WFX4T, manufactured by Japan Polypropylene Corp.) having the meltingpoint of 125° C., MFR (230° C.) of 7 g/10 min, the Vicat softeningtemperature of 113° C., and the tensile modulus of 960 MPa was used.

(A-2) An Isotactic Propylene-Based Polymer (PP1)

A propylene-based polymer (brand name; F327, manufactured by PrimePolymer Co., Ltd.) having MFR (230° C.) of 7 g/10 min, the melting pointof 140° C., the Vicat softening temperature of 123° C., and the tensilemodulus of 1080 MPa was used.

(A-3) An Isotactic Propylene-Based Polymer (PP2)

A propylene-based polymer (brand name; F337D, manufactured by PrimePolymer Co., Ltd.) having MFR (230° C.) of 7 g/10 min, the melting pointof 132° C., the Vicat softening temperature of 115° C., and the tensilemodulus of 910 MPa was used.

(A-4) An Isotactic Propylene-Based Polymer (PP3)

A propylene-based polymer (brand name; XR-110T, manufactured by MitsuiChemicals Inc.) having MFR (230° C.) of 7 g/10 min, the melting point of110° C., the Vicat softening temperature of 85° C., and the tensilemodulus of 380 MPa was used.

TABLE 1 Physical properties of each propylene-based polymer (A) used forExamples Unit (A-1)mPP (A-2)PP1 (A-3)PP2 (A-4)PP3 Melting point Tm ° C.125 140 132 110 Endotherm(140° •H(>140° C.) Presence/ Absence PresencePresence Absence C. or more) Absence Parameter 1 0.234 × (Tm)^(1.277)111.4 128.8 119.5 94.6 Vicat Tv ° C. 113 123 115 85 softeningtemperature Parameter 2 0.902 × (Tm)^(1.011) 118.9 133.3 125.6 104.5Tensile Ym MPa 960 1080 910 380 modulus D1 mW 5.61 4.83 4.78 2.39 D2 mW−0.11 4.49 0.32 −0.05 D2/D1 −0.02 0.93 0.07 −0.02Propylene-Based Copolymers (B)(B) Propylene-Butene-Ethylene Random Copolymer (iPBER)

Ethylene content=14.0 mol %, 1-butene content=20 mol %, MFR (230°C.)=8.5 g/10 min, the melting point=not observed, the molecular weightdistribution (Mw/Mn)=2.0, the Shore A hardness=38, the mm value=90%.

Meanwhile, the propylene-ethylene-1-butene copolymer used for thepresent invention was obtained by the following manner.

Into a 2000-mL polymerization equipment which was fully purged with anitrogen gas, 917 mL of dry hexane, 90 g of 1-butene, andtriisobutylaluminum (1.0 mmol) were charged at room temperature, thenthe inner temperature of the equipment was raised to 65° C., andpropylene was charged till 0.77 MPa, followed by ethylene till 0.79 MPato control the inner pressure. Then,dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconiumdichloride and a toluene solution of methylaluminoxane (manufactured byTosoh Finechem Corp.) were mixed to obtain the toluene solutioncontaining aluminum atom and zirconium atom at the ratio of aluminumatom/zirconium atom=300/1 (molar ratio). Then, the toluene solution wastaken in such an amount that contains 0.002 mmol of zirconium atom(namely 0.6 mmol of aluminum atom was contained), and was charged intothe polymerization reactor, then the polymerization was carried out for20 minutes at the inner temperature of 65° C. with maintaining the innerpressure at 0.79 MPa with ethylene. The polymerization was terminated byadding 20 mL of methanol, the reactor was depressurized, then thepolymer was precipitated from the polymerization solution in 2 L ofmethanol, and then it was dried at 130° C. under vacuum for 12 hours.The amount of the obtained polymer was 60.4 g.

(C) Ethylene-Vinyl Acetate Copolymer (EVA)

Density=950 kg/m³, vinyl acetate content=28% by weight, MFR (190° C.)=15g/10 min, melting point=71° C.

-   (M) Light stabilizer (HALS) Seesorb 102-   (N) UV absorber Sanol 770-   (X) Silane coupling agent (VMMS)-   3-Methacryloxypropyltrimethoxysilane (VMMS), SZ-6030, manufactured    by Dow Corning Toray Co., Ltd.-   (Y) Organic peroxide (PH25B)-   Dialkyl-type peroxide (Perhexa 25B, manufactured by NOF Corporation)-   (Z) Auxiliary agent (TAIC)-   Triallyl isocyanuarate (TAIC) (trade name M-60 (TAIC content 60%),    manufactured by Nippon Kasei Chemical Co., Ltd.) of 0.2 part by    weight (namely 0.12 part by weight as the TAIC content)    Methods for Measuring Physical Properties of the Above-Mentioned Raw    Materials    (1) Melting Point and Confirmation of Presence or Absence of the    Endotherm at 140° C. or More    1-1) Melting Point    From the measured exothermic and endothermic curves, the maximum    melting peak temperature during heating was taken as Tm. The    measurement was performed as follows: after a sample was packed in    an aluminum pan, (i) it was heated to 200° C. at a heating rate of    100° C./min and kept at 200° C. for 5 minutes, (ii) cooled to    −150° C. at 20° C./min, and then (iii) heated to 200° C. at a    heating rate of 20° C./min. The temperature at the endothermic peak    observed in the above (iii) was taken as Tm.    1-2) Confirmation of Presence or Absence of the Endotherm at 140° C.    or More (see FIG. 1)

Dried alumina packed in the same aluminum pan as the one described abovein 1-1) was prepared as the reference, and then the vertical axis value(heat quantity) of the endothermic curve in (iii) obtained by themeasurement according to the conditions of the above-mentioned 1-1) wastaken as follows.

D_(top)=the vertical axis value at the peak position of melting point(maximum melting point)

D₁₄₀° C.=the vertical axis value at 140° C.

D₁₅₀° C.=the vertical axis value at 150° C.

From these values, D1 and D2 defined as below were calculated to confirmwhether they satisfy Equation (1) or not.D1=D _(top) −D ₁₅₀° C.D2=D ₁₄₀° C.−D ₁₅₀° C.D2/D1≦0.05  Equation (1)(2) Contents of Comonomers (Ethylene, 1-Butene)

They were measured by the ¹³C-NMR spectrum analyses.

(3) MFR

MFR was measured at 190° C. or 230° C. under a load of 2.16 kg inaccordance with ASTM D1238.

(4) Vicat Softening Temperature

The measurement was performed in accordance with ASTM D1525.

(5) Density

The density was measured in accordance with the method described in ASTM1505.

(6) Shore A Hardness

A sample sheet with 2 mm thickness was kept at room temperature for 48hours after the measurement, then it was contacted with a push pin ofA-type instrument to read the scale immediately (in accordance with ASTMD2240).

(7-1) Tensile Modulus (a Propylene-Based Polymer (A))

The measurement was performed at 23° C. with the chuck distance of 80 mmand tensile rate of 200 mm/min by using a dumbbell in accordance withJIS K7113-2. The sample for the measurement was the press sheet that wasobtained by hot-pressing a sample at 190° C. between the upper and thelower SUS molds with 4-mm thickness, then rapidly cooling it with acooling chiller of 20° C. for molding, then leaving it for 72 hours orlonger.

(7-2) Tensile Modulus (a Propylene-Based Copolymer (B))

The measurement was performed at 23° C. with the span distance of 30 mmand tensile rate of 200 mm/min by using a JIS3 dumbbell in accordancewith JIS K6301.

The sample for the measurement was the press sheet that was obtained byhot-pressing a sample at 190° C. between the upper and the lower SUSmolds with 4-mm thickness, then rapidly cooling it with a coolingchiller of 20° C. for molding.

(8) Molecular Weight Distribution (Mw/Mn)

The measurement was performed by a Gel Permeation Chromatography (GPC)at the column temperature of 140° C. by using an o-dichlorobenzenesolvent (mobile phase) (Mw; weight-average molecular weight, Mn;number-average molecular weight, relative to polystyrene standards).Specifically, the molecular weight distribution was measured by using agel permeation chromatograph Alliance GPC-2000 manufactured by WatersCorporation in the following manner. Separation columns: two TSKgelGNH6-HT columns and two TSKgel GNH6-HTL columns, all having a columndiameter of 7.5 mm and a column length of 300 mm; column temperature:140° C.; mobile phase: an o-dichlorobenzene (Wako Pure ChemicalIndustries, Ltd.) containing 0.025% by weight of BHT (TakedaPharmaceutical Co., Ltd.) as an antioxidant; moving rate: 1.0 mL/min;sample concentration: 15 mg/10-milliliters; injection volume: 500microliters; detector: a differential refractometer; standardpolystyrenes: polystyrene with Mw<1000 and Mw>4×10⁶ manufactured byTosoh Corp., and polystyrene with 1000≦Mw≦4×10⁶ manufactured by PressureChemical Co.

Evaluation of Suitability for the Thermal Lamination at Low Temperature

Examples 1, 2, 3, and Comparative Examples 1, 2

The raw materials in the composition with a blend ratio as shown inTable 2 were simultaneously charged into a Labo Plastomill (manufacturedby Toyo Seiki Seisaku-sho, Ltd.) and melt kneaded (heated at 190° C. for3 minutes with agitation speed of 40 rpm) to obtain a thermoplasticresin composition. It was press molded (heated at 190° C. for 7 minutesand then cooled, using a Teflon (registered trade name) sheet (300·mthickness) as a mold releasing film) by using a press molding machine toobtain a press sheet (reference) with 0.5 mm thickness.

This press sheet (reference) was heated again at 150° C. or 160° C. for10 minutes (in the same press mold as the one used at 190° C. for themolding of the first sheet, using a Teflon (registered trade name) sheetas a mold releasing film in the similar manner) by using a press moldingmachine to obtain a sample press sheet (reheated) with 0.5 mm thickness.The evaluation results of MFR, the light transmittance, and presence orabsence of cloudiness are shown in Table 2.

Comparative Example 3

The raw material resin composition as shown in Table 2 wassimultaneously charged into a Labo Plastomill (manufactured by ToyoSeiki Seisaku-sho, Ltd.) and melt kneaded (at 110° C. for 3 minutes withagitation speed of 40 rpm) to obtain a thermoplastic resin composition.The thermoplastic resin composition was press molded (at 120° C.) byusing a press molding machine to obtain a press sheet (reference) with0.5 mm thickness.

This press sheet was heated at 150° C. or 160° C. for 20 minutes byusing the same press molding machine to obtain a sample press sheet(reheated) with 0.5 mm thickness. The evaluation results of MFR, thelight transmittance, and presence or absence of cloudiness are shown inTable 2.

TABLE 2 Example 1 Example 2 A-1 mPP % by weight 20 50 B PBER % by weight80 50 C EVA % by weight M Light stabilizer Parts by 0.2 0.2 weight*¹ NUV absorber Parts by 0.1 0.1 weight*¹ X VMMS Parts by 0.5 0.5 weight*¹ YPH25B Parts by 0.06 0.06 weight*¹ Z TAIC Parts by 0.02 0.02 weight*¹Reference MFR g/10 min 29 27 Light % 96 93 transmittancePresence/Absence Eye judgment • • of Cloudiness Heated at 150° C.*² MFRg/10 min 26 28 (atmospheric Light % 95 93 pressure) transmittancePresence/Absence Eye judgment • • of Cloudiness Heated at 160° C.*² MFRg/10 min 26 28 (atmospheric Light % 96 92 pressure) TransmittancePresence/Absence Eye Judgment • • of Cloudiness *¹Parts by weight:blending amount relative to 100 parts by weight of the sum of componentsA to C. *²10 minutes for Examples 1 and 2. Comparative ComparativeComparative Example 1 Example 2 Example 3 Example 3 A-2 PP1 % by weight20 A-3 PP2 % by weight 20 A-4 PP3 % by weight 20 B PBER % by weight 8080 80 C EVA % by weight 100 M Light stabilizer Parts by 0.2 0.2 0.2 0.2weight*¹ N UV absorber Parts by 0.1 0.1 0.1 0.1 weight*¹ X VMMS Parts by0.5 0.5 0.5 0.5 weight*¹ Y PH25B Parts by 0.06 0.06 0.06 0.06 weight*¹ ZTAIC Parts by 0.02 0.02 0.02 weight*¹ Reference MFR g/10 min 26 27 25 15Light % 96 95 96 95 transmittance Presence/Absence Eye judgment • • • •of Cloudiness Heated at MFR g/10 min 28 27 31 No flow 150° C.*² Light %86 90 89 95 (atmospheric transmittance pressure) Presence/Absence Eyejudgment X X X • of Cloudiness Heated at MFR g/10 min 26 27 30 No flow160° C.*² Light % 90 93 95 94 (atmospheric Transmittance pressure)Presence/Absence Eye Judgment • • • • of Cloudiness *¹Parts by weight:blending amount relative to 100 parts by weight of the sum of componentsA to C. *²10 minutes for Comparative Examples 1 and 2 and Example 3, and20 minutes for Comparative Example 3.

From the results shown in Table 2, it was confirmed that by using thethermoplastic resin composition of the present invention a transparentsheet with no cloudiness could be obtained even when heated at lowtemperature. Further, flowability of the resin was not impaired.

Evaluation of Heat Resistance and Glass-Adhesiveness

Example 11

An aluminum plate with 300·m thickness which is used as a quasi modulewas sealed between two press sheets (molded at 190° C.) with 0.5 mmthickness prepared by the method described in Example 1, and further aglass plate with 3 mm thickness and a PET film (white color) with 50·mthickness were laid on it and then laminated by heat (at 150° C. for 10minutes, atmospheric pressure) to obtain a sample (FIG. 6) for the testof the heat resistance. Also a glass plate with 3 mm thickness and apress sheet with 0.5 mm thickness were laminated by heat (at 150° C. for10 minutes, atmospheric pressure) to obtain a sample (FIG. 7) for thetest of the adhesiveness to a glass.

The evaluation results of these are shown in Table 3.

Comparative Example 11

An aluminum plate with 300·m thickness which is used as a quasi modulewas sealed between two press sheets (molded at 140° C.) with 0.5 mmthickness prepared by the method described in Comparative Example 1, andfurther a glass plate with 3 mm thickness and a PET film (white color)with 50·m thickness were laid on it and then laminated by heat (at 150°C. for 10 minutes, atmospheric pressure) to obtain a sample (FIG. 6) forthe test of the heat resistance. Also a glass plate with 3 mm thicknessand a press sheet with 0.5 mm thickness were laminated by heat (at 150°C. for 10 minutes, atmospheric pressure) to obtain a sample (FIG. 7) forthe test of adhesiveness to a glass.

The evaluation results of these are shown in Table 3.

TABLE 3 Example Comparative 11 Example 11 A-1 mPP % by weight 20 A-2 rPP% by weight B PBER % by weight 80 C EVA % by weight 100 M Lightstabilizer Parts by weight*¹ 0.2 0.2 N UV absorber Parts by weight*¹ 0.10.1 X VMMS Parts by weight*¹ 0.5 0.5 Y PH25B Parts by weight*¹ 0.06 0.06Z TAIC Parts by weight*¹ 0.02 Heat resistance Eye judgment No flow Noflow Glass-adhesion strength N/cm 19 16 *¹Parts by weight: blendingamount relative to 100 parts by weight of the sum of components A to C.

From the results in Table 3, it was confirmed that the thermoplasticresin composition of the present invention had sufficiently good heatresistance for practical use without crosslinking that might causeimpairing the fluidity, and in addition, the thermoplastic resincomposition of the present invention had sufficiently good adhesionstrength to a glass for practical use.

Examples 4 and 5, Reference Example 1

As propylene-based polymer (AA), the propylene-based polymer (A-5) wasused in Examples 4 and 5 and the propylene-based polymer (A-6) inReference Example 1.

Propylene-Based Polymers (AA)

(A-5) Metallocene Isotactic Random Polypropylene (mPP)

Melting point=125° C., MFR (230° C.)=7 g/10 min, Mw/Mn=2.1, ethylenecontent=4.6 mol %, mm=95% This propylene-based polymer (A-5) wasobtained by copolymerizing propylene with ethylene in the presence ofthe metallocene catalyst comprisingdiphenylmethylene(3-t-butyl-5-methylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride and methylaluminoxane.

(A-6) Isotactic Random Polypropylene (rPP)

MFR (230° C.)=7 g/10 min, melting point=140° C., Mw/Mn=4.8, mm=97%

The raw materials with a blend ratio as shown in Table weresimultaneously charged into a Labo Plastomill (manufactured by ToyoSeiki Seisaku-sho, Ltd.) and melt kneaded (at 190° C. for 3 minutes withagitation speed of 40 rpm) to obtain a thermoplastic resin composition.It was press molded (heated at 190° C. for 7 minutes and then cooled, byusing Lumiror (manufactured by Toray Industries, Inc., 100·m thickness)as a mold releasing film) to obtain a press sheet (reference) with 0.5mm thickness.

This press sheet was further heated at 150° C. or 160° C. for 10 minutes(in the same press mold as the one used at 190° C. for the molding ofthe first sheet) to obtain a sample press sheet with 0.5 mm thickness.The evaluation results of MFR, light transmittance, and presence orabsence of the cloudiness are shown in Table 4.

Comparative Example 4

The raw materials as shown in Table 4 were simultaneously charged into aLabo Plastomill (manufactured by Toyo Seiki Seisaku-sho, Ltd.) and meltkneaded (at 110° C. for 3 minutes with agitation speed of 40 rpm) toobtain a thermoplastic resin composition. It was press molded (at 140°C.) by using a press molding machine to obtain a press sheet (reference)with 0.5 mm thickness.

This press sheet was further heated at 150° C. or 160° C. for 20 minutesby using the same press molding machine as before to obtain a samplepress sheet with 0.5 mm thickness. The evaluation results of MFR, lighttransmittance, and presence or absence of the cloudiness are shown inTable 4.

TABLE 4 Example Example Reference Comparative 4 5 Example 1 Example 4A-5 mPP % by 20 50 weight A-6 rPP % by 20 weight B PBER % by 80 50 80weight C EVA % by 100 weight M Light stabilizer Parts by 0.2 0.2 0.2 0.2weight*¹ N UV absorber Parts by 0.1 0.1 0.1 0.1 weight*¹ X VMMS Parts by0.5 0.5 0.5 0.5 weight*¹ Y PH25B Parts by 0.06 0.06 0.06 0.06 weight*¹ ZTAIC Parts by 0.02 0.02 0.02 weight*¹ Reference MFR g/10 min 29 27 26 15Light % 93 92 93 93 transmittance Presence/Absence Eye • • • • ofcloudiness judgment Heated at MFR g/10 min 28 28 28 No flow 150° C.*²Light % 92 92 86 92 (atmospheric transmittance pressure)Presence/Absence Eye • • X • of cloudiness judgment Heated at MFR g/10min 29 28 26 No flow 160° C.*² Light % 93 91 90 92 (atmosphericTransmittance pressure) Presence/Absence Eye • • • • of cloudinessJudgment *¹Parts by weight: blending amount relative to 100 parts byweight of the sum of components A to C. *²10 minutes for Examples 4 and5 and Reference Example 1, and 20 minutes for Comparative Example 4.

From the results shown in Table 4, it was confirmed that by using thethermoplastic resin composition of the present invention, a transparentsheet with no cloudiness could be obtained even when heated at lowtemperature and non-crosslinked.

Evaluation of Heat Resistance and Glass-Adhesiveness

Example 41

An aluminum plate with 300·m thickness which is used as a quasi module,was sealed between two press sheets (molded at 190° C.) with 0.5 mmthickness prepared by the method described in Example 4, and further aglass plate with 3 mm thickness and a PET film (white color) with 50·mthickness were laminated by heat (at 150° C. for 10 minutes, atmosphericpressure) to obtain a sample (FIG. 6) for the test of the heatresistance, and a glass plate with 3 mm thickness and a press sheet with0.5 mm thickness were laid on it and then laminated by heat (at 150° C.for 10 minutes, atmospheric pressure) to obtain a sample (FIG. 7) forthe test of the adhesiveness to a glass.

The evaluation results are shown in Table 5.

Comparative Example 41

An aluminum plate with 300·m thickness which is used as a quasi module,was sealed between two press sheets (molded at 140° C.) with 0.5 mmthickness prepared by the method described in Comparative Example 4, andfurther a glass plate with 3 mm thickness and a PET film (white color)with 50·m thickness were laid on it and then laminated by heat (at 150°C. for 10 minutes, atmospheric pressure) to obtain a sample (FIG. 6) forthe heat resistance test, and a glass plate with 3 mm thickness and apress sheet with 0.5 mm thickness were laminated by heat (at 150° C. for10 minutes, atmospheric pressure) to obtain a sample (FIG. 7) for thetest of the adhesiveness to a glass.

The evaluation results are shown in Table 5.

TABLE 5 Example Comparative 41 Example 41 A-5 mPP % by weight 20 A-6 rPP% by weight B PBER % by weight 80 C EVA % by weight 100 M Lightstabilizer Parts*¹ by weight*¹ 0.2 0.2 N UV absorber Parts by weight*¹0.1 0.1 X VMMS Parts by weight*¹ 0.5 0.5 Y PH25B Parts by weight*¹ 0.060.06 Z TAIC Parts by weight*¹ 0.02 Heat resistance Eye judgment No flowNo flow Glass-adhesion strength N/cm 19 16 *¹Parts by weight: blendingamount relative to 100 parts by weight of the sum of components A to C.

From the results in Table 5, it was confirmed that the thermoplasticresin composition of the present invention can exert sufficiently goodheat resistance and glass adhesion strength for practical use.

1. A thermoplastic resin composition, prepared by a method comprisingmelt kneading a mixture of 1 to 95% by weight of a propylene-basedpolymer (A) and 5 to 99% by weight of a propylene-based copolymer (B),which is a copolymer of propylene and at least one α-olefin having 2 to20 carbon atoms other than propylene, wherein the sum of (A) and (B) is100% by weight, in the presence of an organic peroxide with a couplingagent (Y), wherein the amount of Y is 0.1 to 5 parts by weight relativeto total 100 parts by weight of (A) and (B), and wherein (A) satisfiesthe following (i) and (ii), and (B) does not show a melting point asmeasured by a differential scanning calorimeter (DSC): (i) a meltingpoint measured by a differential scanning calorimeter (DSC) method is inthe range of 80 to 135° C.; and (ii) an endotherm attributable tocrystal melting is not observed at 140° C. or more in the endothermiccurve measured by a differential scanning calorimeter (DSC) method. 2.The thermoplastic resin composition according to claim 1, wherein thepropylene-based polymer (A) further satisfies the following (iii): (iii)a melting point (Tm) measured by a differential scanning calorimeter(DSC) and Vicat softening temperature (Tv) measured in accordance withASTM D1525 satisfy Equation (I)0.234×(Tm)^(1.277) <Tv<Tm,  Equation (1), wherein Tm is in the range of80 to 135° C.
 3. The thermoplastic resin composition according to claim1, wherein the propylene-based copolymer (B) is apropylene-ethylene-α-olefin copolymer (B-1), which comprises 45 to 92mol % of the constituent unit derived from propylene, 5 to 25 mol % ofthe constituent unit derived from ethylene, and 3 to 30 mol % of theconstituent unit derived from an α-olefin having 4 to 20 carbon atoms,and has no melting point as observed by a differential scanningcalorimeter.
 4. The thermoplastic resin composition according to claim1, wherein a melt flow rate of the composition at 230° C. is 0.05 g/10min or more.